JPS6211071B2 - - Google Patents
Info
- Publication number
- JPS6211071B2 JPS6211071B2 JP16619780A JP16619780A JPS6211071B2 JP S6211071 B2 JPS6211071 B2 JP S6211071B2 JP 16619780 A JP16619780 A JP 16619780A JP 16619780 A JP16619780 A JP 16619780A JP S6211071 B2 JPS6211071 B2 JP S6211071B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- etching
- transparent conductive
- conductive film
- etchant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000005530 etching Methods 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 13
- 229910001887 tin oxide Inorganic materials 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910003437 indium oxide Inorganic materials 0.000 description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 108010088694 phosphoserine aminotransferase Proteins 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- -1 sodium citrate Chemical class 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- ing And Chemical Polishing (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Weting (AREA)
Description
本発明は透明導電膜のエツチング液つまりエツ
チヤントに関するものである。
透明導電膜は最近、液晶表示、EL、EPID、コ
ロイダルライトバルブ、EC等のデイスプレイ用
電極として、フオトセルや太陽電池の電極として
広く用いられるようになつた。特に前者のデイス
プレイ用電極として用いられる場合通常パターニ
ングされて用いられる。このようなパターニング
された透明導電膜をいかに安価に、安定に作るか
が問題となつている。つまり、透明導電膜には酸
化インジウム系（酸化インジウム又はそれに四価
金属酸化物例えばSnO2等をドープしたもの）と
酸化スズ系（酸化スズ又はそれに五価金属酸化物
例えばSb2O5等をドープしたもの）がある。
表１は酸化インジウム系と酸化スズ系の透明導
電
The present invention relates to an etching solution or etchant for transparent conductive films. Transparent conductive films have recently come to be widely used as electrodes for displays such as liquid crystal displays, EL, EPID, colloidal light valves, and EC, and as electrodes for photocells and solar cells. In particular, when used as a display electrode in the former case, it is usually used after being patterned. The problem is how to make such a patterned transparent conductive film inexpensively and stably. In other words, the transparent conductive film contains indium oxide (indium oxide or doped with a tetravalent metal oxide such as SnO 2 ) and tin oxide (tin oxide or doped with a pentavalent metal oxide such as Sb 2 O 5 ). There is a doped version). Table 1 shows the transparent conductivity of indium oxide and tin oxide.
【表】
膜の各種性質を比較したものである。酸化インジ
ウム系は抵抗も低くエツチング性も良い。（温塩
酸とか塩化第一鉄を含んだ塩酸で容易に浸漬エツ
チングできる）が、製造方法がバツチ処理になる
ためコストが高くなつていた。又デイスプレイ用
電極に用いるとき、電気化学的安定性が悪いた
め、SiO2のような無機物とかポリイミドのよう
な有機物でコーテイングして用いる必要があつ
た。１方酸化スズ系は無水塩化第二スズから
CVD法（Sb2O5のドープは無水五塩化アンチモン
から）で安価に得られ、抵抗も五酸化アンチモン
のドープにより酸化インジウム並のものが得られ
るが唯一の欠点はエツチング性である。従来は
Zn粉末をふりかけ、その上に塩酸をシヤワー、
ハケ等でコスリ落としていた。この方法はハケコ
スリという物理的手段が加わるため、パターニン
グする時のレジストのハク離等を促進し、ピンホ
ール、切れ、オーバーエツチング等の問題を引き
おこしていた。１方浸漬エツチング方法として
USP4009061にある二価クロムイオンと三価クロ
ムのレドツクス系を用いるものがある。このエツ
チヤントは、エツチングスピードが遅い、液の劣
化スピードが急速等の大きな問題点を含んでい
る。この二つは全く同等であり、ポテンシヤルエ
ネルギーである二価クロムが液調合の際にも三価
クロムに変化し、エツチング開始時にはレドツク
ス系のポテンシヤルエネルギーが初期から低くな
つていることが考えられる。この二価クロムの三
価クロムへの変化は、１つは空気中の酸素の還元
反応にともなうものであり、１つは二価クロムの
プロトンとの反応による水素発生（Cr2 +＋H+→
Cr3+＋1/2H2）によるものではないかと思われ
る。本発明者は、このようなレドツクス系の酸素
還元反応の過電圧の増加と、水素発生反応の過電
圧増加を検討した結果、有機酸の添加が非常に大
きな効果をもたらすことを発見した。
本発明の目的は、酸化スズ系透明導電膜を浸
漬、シヤワー等の物理的手段を供なわない方法に
より、エツチングスピードが速く、長時間使用で
き、しかも精度の良いエツチング液を得ることに
ある。
本発明に述べる酸化スズ及び酸化スズに五価金
属酸化物をドープした透明導電膜は、例えば
CVD法により、塩化物、又は塩素含有有機金属
化合物をソースとして熱分解することにより得ら
れる。酸化スズソースとしては、無水塩化第２ス
ズ、塩化トリメチルスズ等があげられる。五価酸
化物としては、五酸化アンチモン、五酸化リン等
である。特に前者はよくドーピング剤として用い
られ、0.01〜１モル％ドープされる。約500℃に
加熱した絶縁基板（ガラス、セラミツク等）上に
CVDされた透明導電膜は、フオトレジスト、レ
ジストインクのスクリーン印刷法等により所定の
パターンが形成される。レジストパターニングさ
れた透明導電膜付絶縁基板は、塩酸、臭化水素
酸、ヨウ化水素酸、硝酸、硫酸、リン酸等の無機
酸から選ばれた一種以上を含む0.5N以上の酸性
水溶液中にレドツクス電位−0.20V（v.s.NHE）
以下を有する金属イオンを溶解し、５ｇ／以上
の有機酸を添加したエツチング液中に常温〜90℃
の適当な温度に浸漬、又は液をシヤワー等するこ
とによつて透明導電膜をエツチングする。前記無
機酸で主として用いられるのが塩酸、硝酸、硫
酸、リン酸である。レドツクス電位−0.20V（v.
s.NHE）を有する系とは、Cr2+／Cr3+，Ti2+／
Ti3+，V2+／V3+，Zn2+／Zn3+等である。これら
のレドツクス系は前記無機酸に金属を溶解させる
例えば金属クロムを溶解させるか、価数の大きな
金属塩として溶解し、Zn―HCl系で還元して
（CrCl3の塩酸酸性溶液にZn粉末を添加する。
Ｔ：Cl4の塩酸酸性溶液にZn粉末を添加する）形
成するか、外部電源による電解還元を行なつても
良い。これらは酸化スズの４価が２価イオンにな
るレドツクス電位−0.14V（vs.NHE）より卑な
電位をもつものであれば良い。例えばCrのレド
ツクス系を用いたときのエツチングの全反応は
Cr2+→Cr3+＋ｅ ……(1)
1/2SnO2＋H+＋ｅ
→1/2SnD＋1/2H2O ……(2)
(1)＋(2)
Cr2+＋1/2SnO2＋H+
→Cr3+＋1/2SnO＋1/2H2O ……(3)
1/2SnO＋HCl
→1/2SnCl2＋1/2H2O ……(4)
と思われる。前記したように(1)，(2)の反応と競合
して
Cr2→Cr3＋ｅ ……(5)
1/4O2＋1/2H+＋ｅ→1/2H2O ……(6)
(5)＋(6)
Cr2＋1/4O2＋1/2H+
→Cr3B＋1/2H2O ……(7)
の空気中の酸素の還元反応により２価クロムはど
んどん消費されてしまう。工業的に空気を立ち切
つてエツチングをすることはむずかしい。そこで
本発明者は(6)の反応速度を低下させる、つまり酸
素の還元反応に対する過電圧の大きな添加剤を
種々検討した結果、５ｇ／以上の有機酸が有効
であることを発見した。効果的な有機酸には、酒
石酸、マロン酸、乳酸、ステアリン酸、ピクリン
酸、グルコン酸、コハク酸、クエン酸、永酢酸、
フマル酸、リンゴ酸等であり、場合によつてはこ
れらの塩の形、（例えばクエン酸ナトリウム等）
で添加してもよい。この場合前記酸性溶液のPHが
３以上にならないようにしなければならない。
以下実施例によつて本発明を詳細に説明する。
実施例 １
ホウケイ酸系ガラス基板にCVD法を用いて、
基板を500℃に加熱しながら無水塩化第２スズの
ベイパーを用い、SnO2透明導電膜300Åの厚みに
形成した。ネガ型フオトレジストをロールコータ
ーで塗布し所定のガラスマスクを用い露光現象し
た。次に6N塩酸100c.c.にクエン酸を40ｇ加熱しな
がら溶解した。完全溶解したら金属クロムを0.6
ｇ添加し60℃で約５分間水素を発生しながら溶解
した。このエツチヤントを用い前記フオトパター
ニングされた酸化スズ透明導電膜付ガラス基板を
浸漬した。約10秒間で透明導電膜は完全にエツチ
ングされた。
比較例
実施例１でエツチヤント中にクエン酸を添加し
ない場合約40秒後にエツチングされた。第１図は
実施例１のエツチヤント及び比較例のエツチヤン
トの各種温度におけるエツチングスピードを示し
たものである。第１図で１は実施例１の本発明の
エツチヤント、２は比較例のエツチヤントのエツ
チングスピードを示す。
実施例 ２
実施例１において酸化スズに五酸化アンチモン
を0.1モル％添加した透明導電膜を用いた。第１
図の３及び４はこの透明導電膜のエツチングスピ
ードを示したものであり、３は本発明品、４は前
述比較例のエツチヤントのエツチングスピードを
示す。
第１図によつて本発明品のエツチングスピード
は従来品より非常に速くなつていることがわか
る。
第２図はこのようなエツチヤントを60℃に保持
した場合のエツチングスピードの経時的変化を示
す。第２図より本発明品は60℃に放置しても液の
劣化スピードが格段に遅いことがわかる。第２図
の６は本発明のエツチヤント、５は比較例のエツ
チヤントを示す。
実施例 ３
実施例１において透明導電膜のパターン幅10μ
ピツチ15μで長さ５cmのパターニングを行なつ
た。従来行なわれているZn―HCl系のハケコスリ
法によるエツチングではパターン数100本中88本
が断線していた。比較例１のエツチングでは100
本中48本が断線、エツチング不足によるシヨート
が20本あつた。１方本発明によるエツチングでは
切れは100本中わずかに１本であり、シヨートは
全くなかつた。有機酸の添加により液の表面張力
が低くなり表面のぬれがよくなりエツチング精度
が向上したものと思われる。
以上実施例に従つて説明したが本発明のエツチ
ヤントは酸化インジウム系透明導電膜にも応用で
きることは明らかである。
本発明のエツチヤントによつてパターニングさ
れた透明導電膜は液晶、EC、EPIP、コロイダル
ライトバルブ等の表示体、フオトセル、太陽電池
等の電極として用いることができる。[Table] Comparison of various properties of membranes. Indium oxide type materials have low resistance and good etching properties. (It can be easily immersed in etching using warm hydrochloric acid or hydrochloric acid containing ferrous chloride.) However, the production method involves batch processing, which increases costs. Furthermore, when used in display electrodes, it was necessary to coat it with an inorganic material such as SiO 2 or an organic material such as polyimide because of its poor electrochemical stability. Unilateral tin oxide system is made from anhydrous stannic chloride.
It can be obtained inexpensively by the CVD method (Sb 2 O 5 doping is from anhydrous antimony pentachloride), and resistance comparable to that of indium oxide can be obtained by doping antimony pentoxide, but the only drawback is etching properties. conventionally
Sprinkle Zn powder, shower hydrochloric acid on top,
I had scrubbed it off with a brush, etc. This method involves the physical means of brushing and scraping, which promotes peeling of the resist during patterning, causing problems such as pinholes, cuts, and over-etching. As a one-way immersion etching method
There is one that uses a redox system of divalent chromium ions and trivalent chromium as described in USP4009061. This etchant has major problems such as slow etching speed and rapid deterioration of the solution. These two are completely equivalent, and it is thought that divalent chromium, which is the potential energy, changes to trivalent chromium during liquid preparation, and the potential energy of the redox system is initially low at the start of etching. This change from divalent chromium to trivalent chromium is due to the reduction reaction of oxygen in the air, and hydrogen generation due to the reaction of divalent chromium with protons (Cr 2 + +H + →
This is thought to be due to Cr 3+ +1/2H 2 ). The present inventor investigated the increase in overvoltage of such a redox-based oxygen reduction reaction and the increase in overvoltage of a hydrogen generation reaction, and as a result, discovered that the addition of an organic acid has a very large effect. An object of the present invention is to obtain an etching solution that can be used for a long time, can be used for a long time, and has high accuracy by a method that does not require physical means such as dipping or showering a tin oxide-based transparent conductive film. The transparent conductive film of tin oxide and tin oxide doped with a pentavalent metal oxide described in the present invention is, for example,
It is obtained by thermal decomposition using a chloride or a chlorine-containing organometallic compound as a source using the CVD method. Examples of the tin oxide source include anhydrous stannic chloride, trimethyltin chloride, and the like. Examples of pentavalent oxides include antimony pentoxide and phosphorus pentoxide. In particular, the former is often used as a doping agent and is doped with 0.01 to 1 mol%. on an insulating substrate (glass, ceramic, etc.) heated to approximately 500°C.
A predetermined pattern is formed on the CVD transparent conductive film using photoresist, resist ink screen printing, or the like. The resist-patterned insulating substrate with a transparent conductive film is placed in an acidic aqueous solution of 0.5N or more containing one or more types of inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, and phosphoric acid. Redox potential −0.20V (vsNHE)
Dissolve the following metal ions in an etching solution containing 5 g/or more of an organic acid at room temperature to 90°C.
The transparent conductive film is etched by dipping it at an appropriate temperature or by showering it with a solution. Hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid are mainly used as the inorganic acids. Redox potential −0.20V (v.
s.NHE) is a system with Cr 2+ /Cr 3+ , Ti 2+ /
These include Ti 3+ , V 2+ /V 3+ , Zn 2+ /Zn 3+ and the like. These redox systems dissolve metals in the above-mentioned inorganic acids, such as dissolving metal chromium, or dissolving it as a metal salt with a high valence, and reducing it with a Zn-HCl system (Zn powder is dissolved in an acidic solution of CrCl3 in hydrochloric acid). Added.
T: Adding Zn powder to an acidic solution of Cl 4 in hydrochloric acid) or electrolytic reduction using an external power source may be performed. These may have a potential less noble than the redox potential -0.14 V (vs.NHE) at which tetravalent tin oxide becomes a divalent ion. For example, the total etching reaction when using a Cr redox system is Cr 2+ →Cr 3+ +e ...(1) 1/2SnO 2 +H + +e →1/2SnD+1/2H 2 O ...(2) (1 )＋(2) Cr 2+ +1/2SnO 2 +H + →Cr 3+ +1/2SnO＋1/2H 2 O ……(3) 1/2SnO＋HCl →1/2SnCl 2 +1/2H 2 O …(4) It can be done. As mentioned above, Cr 2 →Cr 3 +e ...(5) 1/4O 2 +1/2H + +e→1/2H 2 O ...(6) (5 )+(6) Cr 2 +1/4O 2 +1/2H + →Cr 3B +1/2H 2 O ...(7) Due to the reduction reaction of oxygen in the air, divalent chromium is rapidly consumed. It is difficult to perform etching by cutting off the air in an industrial manner. Therefore, the present inventor investigated various additives that reduce the reaction rate (6), that is, has a large overvoltage for the oxygen reduction reaction, and found that 5 g/or more of an organic acid is effective. Effective organic acids include tartaric acid, malonic acid, lactic acid, stearic acid, picric acid, gluconic acid, succinic acid, citric acid, acetic acid,
fumaric acid, malic acid, etc., sometimes in the form of their salts (e.g. sodium citrate, etc.)
It may be added with In this case, the pH of the acidic solution must not exceed 3. The present invention will be explained in detail below with reference to Examples. Example 1 Using the CVD method on a borosilicate glass substrate,
A SnO 2 transparent conductive film was formed to a thickness of 300 Å using an anhydrous stannic chloride vapor while heating the substrate to 500°C. A negative type photoresist was applied using a roll coater and exposed using a predetermined glass mask. Next, 40 g of citric acid was dissolved in 100 c.c. of 6N hydrochloric acid while heating. After completely melting, add 0.6% of metallic chromium.
g was added and dissolved at 60°C for about 5 minutes while generating hydrogen. Using this etchant, the photo-patterned glass substrate with a tin oxide transparent conductive film was immersed. The transparent conductive film was completely etched in about 10 seconds. Comparative Example When citric acid was not added to the etchant in Example 1, etching occurred after about 40 seconds. FIG. 1 shows the etching speed of the etchant of Example 1 and the etchant of Comparative Example at various temperatures. In FIG. 1, 1 indicates the etching speed of the etchant of the present invention of Example 1, and 2 indicates the etching speed of the etchant of the comparative example. Example 2 In Example 1, a transparent conductive film in which 0.1 mol% of antimony pentoxide was added to tin oxide was used. 1st
3 and 4 in the figure show the etching speed of this transparent conductive film, 3 shows the etching speed of the etchant of the present invention, and 4 shows the etching speed of the etchant of the above-mentioned comparative example. It can be seen from FIG. 1 that the etching speed of the product of the present invention is much faster than that of the conventional product. FIG. 2 shows the change in etching speed over time when such an etchant is maintained at 60°C. From FIG. 2, it can be seen that the rate of deterioration of the liquid in the product of the present invention is significantly slow even when left at 60°C. In FIG. 2, 6 shows an etchant of the present invention, and 5 shows an etchant of a comparative example. Example 3 In Example 1, the pattern width of the transparent conductive film was 10μ
Patterning was performed with a pitch of 15μ and a length of 5cm. In the conventional Zn-HCl-based etching method, 88 wires out of 100 were broken. 100 for the etching of Comparative Example 1
48 of the wires were broken, and 20 were shot due to insufficient etching. On the other hand, with the etching according to the present invention, only 1 out of 100 pieces was cut, and there were no shoots at all. It is believed that the addition of the organic acid lowered the surface tension of the liquid, resulting in better surface wetting and improved etching accuracy. Although the embodiments have been described above, it is clear that the etchant of the present invention can also be applied to indium oxide-based transparent conductive films. A transparent conductive film patterned with the etchant of the present invention can be used as an electrode for displays such as liquid crystals, ECs, EPIPs, colloidal light valves, photocells, solar cells, etc.
第１図……エツチング温度とエツチングスピー
ドの関係を示す。第２図……従来品と本発明品の
エツチヤントの60℃におけるエツチング速度の変
化を示す。
Figure 1 shows the relationship between etching temperature and etching speed. Figure 2 shows the change in etching rate at 60°C of the etchants of the conventional product and the product of the present invention.
Claims (1)
ープした透明導電膜をエツチングする場合に、塩
酸、臭化水素酸、ヨウ化水素酸、硝酸、硫酸、リ
ン酸等の無機酸から選ばれた１種以上を含む
0.5N以上の酸性水溶液にレドツクス電位−0.2V
（ｖ・ｓ NHE）以下を有する金属イオンを溶解
し、さらに、５ｇ／以上の有機酸を含んでなる
ことを特徴とする透明導電膜のエツチヤント。1. When etching a transparent conductive film made of tin oxide and tin oxide doped with a pentavalent metal oxide, an inorganic acid selected from hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, phosphoric acid, etc. Contains one or more types
Redox potential -0.2V for acidic aqueous solutions of 0.5N or higher
An etchant for a transparent conductive film, characterized in that it dissolves metal ions having (v·s NHE) or less, and further contains 5 g/or more of an organic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16619780A JPS5789480A (en) | 1980-11-26 | 1980-11-26 | Etchant for transparent electric conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16619780A JPS5789480A (en) | 1980-11-26 | 1980-11-26 | Etchant for transparent electric conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5789480A JPS5789480A (en) | 1982-06-03 |
| JPS6211071B2 true JPS6211071B2 (en) | 1987-03-10 |
Family
ID=15826883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16619780A Granted JPS5789480A (en) | 1980-11-26 | 1980-11-26 | Etchant for transparent electric conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5789480A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61145529A (en) * | 1984-12-19 | 1986-07-03 | Matsushita Electric Ind Co Ltd | Formation of transparent electrode pattern |
| EP0617144B1 (en) * | 1993-03-26 | 1997-08-06 | Nippon Paint Co., Ltd. | Use of an aqueous acidic cleaning solution for aluminum and aluminum alloys and process for cleaning the same |
| DE102005035255A1 (en) * | 2005-07-25 | 2007-02-01 | Merck Patent Gmbh | Etching media for oxide, transparent, conductive layers |
-
1980
- 1980-11-26 JP JP16619780A patent/JPS5789480A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5789480A (en) | 1982-06-03 |
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